Investigating deposition sequence during synthesis of Pd/Al2O3 catalysts modified with organic monolayers

Blanchette, Zachary; Zhang, Jing; Yazdi, Sadegh; Griffin, Michael B.; Schwartz, Daniel K.; Medlin, J. Will

doi:10.1039/d1cy02131a

Investigating deposition sequence during synthesis of Pd/Al₂O₃ catalysts modified with organic monolayers

Journal Article · Mon Feb 21 00:00:00 EST 2022 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/d1cy02131a· OSTI ID:1866621

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Univ. of Colorado, Boulder, CO (United States); University of Colorado Boulder
Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Modification of supported metal catalysts with self-assembled monolayers (SAMs) has been shown to improve selectivity and turnover frequencies (TOFs) for many catalytic reactions. However, these benefits are often accompanied by a decrease in overall mass activity due to partial blocking of active sites by the monolayers. Therefore, a potential method for increasing site accessibility is to deposit the active metal (e.g., Pd) after deposition of a SAM modifier on the support material. In this work, Pd/Al₂O₃ catalysts were synthesized using both a conventional, “metal-first” sequence in which the phosphonic acid (PA) SAM was deposited on Pd/Al₂O₃ and a “SAM-first” technique in which the ligands were deposited onto the support prior to deposition of the metal. Although metal-first catalysts showed a significant increase in TOF during benzyl alcohol HDO, they exhibited only a modest increase in overall mass activity due to a decrease in the number of active sites. Meanwhile, SAM-first catalysts showed similar improvements in TOF and toluene selectivity but exhibited significantly improved HDO rates compared to metal-first catalysts. Here, the rate increase was attributed to reduced site blocking as evidenced by CO chemisorption measurements. Additionally, analysis of catalysts having high Pd loadings using transmission electron microscopy (TEM) showed that SAM-first catalysts generally resulted in lower average particle sizes than traditionally modified and unmodified catalysts, suggesting that precoating the support surface with PAs changes the way that Pd is deposited during incipient wetness, leading here to improved activity.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0005239

OSTI ID:: 1866621

Alternate ID(s):: OSTI ID: 1847001
OSTI ID: 1866766

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 7 Vol. 12; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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